Substituted-acetic acid ester

ABSTRACT

A novel substituted-arylacetic acid ester of the formula, ##STR1## wherein R 1  and R 2  are each hydrogen or a halogen atom, a C 1  -C 4  alkyl, C 2  -C 4  alkenyl, C 1  -C 4  alkoxy, cyano, nitro, methylthio, C 1  -C 4  alkanoyl, C 1  -C 4  alkanoyloxy, or C 1  -C 4  alkoxycarbonyl group, or R 1  and R 2 , taken together, may form methylenedioxy, a C 3  -C 5  alkylene or butadienylene (--CH═CH--CH═CH--) ring; R 3  is a C 2  -C 4  alkyl, C 2  -C 4  alkenyl, propargyl, C 3  -C 6  cycloalkyl or cyclopropylmethyl group; R 4  is hydrogen or a halogen atom, methyl or ethyl group; R 5  is allyl, propargyl, 3-butenyl, 3-butynyl, phenyl or benzyl group; and A is oxygen or sulfur atom or --CH═CH-- group, which possesses various useful insecticidal and acaricidal activities and can be prepared by reacting a substituted-arylacetic acid of the formula; ##STR2## wherein R 1 , R 2 , R 3  and A are each as defined above, or a reactive derivative thereof with an alcohol, or halide or sulfonate thereof of the formula, ##STR3## wherein R 4  and R 5  are each as defined above and X is hydroxy group, a halogen atom, alkylsulfonyloxy or arylsulfonyloxy group.

The present invention relates to a novel substituted-arylacetic acidester of the formula (I), ##STR4## wherein R₁ and R₂ are each hydrogenor a halogen atom (preferably fluorine, chlorine or bromine atom), a C₁-C₄ alkyl, C₂ -C₄ alkenyl (preferably vinyl), C₁ -C₄ alkoxy (preferablyC₁ -C₃ alkoxy), cyano, nitro, methylthio, C₁ -C₄ alkanoyl (preferablyacetyl), C₁ -C₄ alkanoyloxy (preferably acetyloxy) or C₁ -C₄alkoxycarbonyl (preferably methoxycarbonyl), or R₁ and R₂, takentogether, may form methylenedioxy, a C₃ -C₅ alkylene (preferably tri- ortetra-methylene) or butadienylene (--CH═CH--CH═CH--) ring; R₃ is a C₂-C₄ alkyl, C₂ -C₄ alkenyl (preferably allyl), propargyl, C₃ -C₆cycloalkyl or cyclopropylmethyl group; R₄ is hydrogen or a halogen atom(preferably chlorine), methyl or ethyl group; R₅ is allyl, propargyl,3-butenyl, 3-butynyl, phenyl or benzyl group; and A is oxygen or sulfuratom or --CH═CH-- group, which possesses various useful insecticidal andacaricidal activities, and also relates to a method for the preparationthereof.

The inventors searched for a novel compound having an insecticidalactivity apart from the existing insecticidally active compounds such asorgano-phosphorus compounds, carbamate compounds, pyrethroidal estergroups, organo-chlorine compounds and the like. As the results, it wasfound that substituted acetic acid esters of aliphatic or aromaticalcohols had a wide range of insecticidal activity. Further, it wasfound that the alcohol moeity of the ester groups which wereconventionally well known as a pyrethroidal insecticide and asubstituted acetic acid provided an ester having both an activitysimilar to that of the conventional pyrethroid and a wider range ofinsecticidal spectrum [British Patent Publication No. 1439615].

Further, the inventors searched in more detail for many homologues ofthe ester compound and investigated their insecticidal activity and use.As the results, it was found that the present esters of the formula (I)were characteristically superior in insecticidal effect, persistency andparticularly rapid effect.

The compounds of the present invention have one asymmetric carbon atomin each of the acid moeity and alcohol moeity and therefore the opticalisomers thereof are also present. Among the combinations of the bothisomeric moeities, the most preferred combination produces aninsecticidal activity of 2 to 6 times as strong as that of the racemate.

The compounds of the present invention contain, of course, opticalisomers in addition to racemates.

The novel substituted-arylacetic acid esters of the formula (I) can beobtained by reacting a substituted-arylacetic acid of the formula (II),##STR5## wherein R₁, R₂ and R₃ are as defined above, or its reactivederivative, with an alcohol halide or sulfonate of the formula (III),##STR6## wherein R₄, R₅ and X is hydroxy group, a halogen atom,alkylsulfonyloxy or arylsulfonyloxy group.

The reactive derivatives of acid referred to herein include acid halide,acid anhydride and alkali metal salt, silver salt and organic tertiaryamine salt thereof and the like.

Methods for the preparation of the present substituted-arylacetic acidesters of the formula (I) will be illustrated in more detail below.

The reaction between the acid and the alcohol is achieved by reactingthe both under suitable dehydration conditions, for example, at roomtemperature or under heating in a suitable inert solvent such asbenzene, toluene or petroleum ether in the presence of a dehydratingagent such as dicyclohexylcarbodiimide.

When an acid halide is used, the present ester is sufficiently obtainedat room temperature in a high yield by reacting the acid halide with thealcohol using organic tertiary amines such as pyridine and triethylamineas a dehydrohalogenating agent. The acid halide used may optionally beselected within a range of the present invention, but an acid chlorideis usually preferred. In this reaction, the presence of solvent is notessential, but it is desirable for the smooth progress of the reactionand an inert solvent such as benzene, toluene, petroleum benzine or thelike is usually used.

Alternatively, when an acid anhydride is used, the reaction can beachieved by reacting the acid anhydride with the alcohol at roomtemperature without particular reaction assistant. In this case, heatingof the reaction system and the use of an inert solvent such as tolueneor xylene are desirable for the smooth progress of the reaction, butthey are not essential. When the corresponding halide or sulfonate ofthe alcohol is used, the acid is used in the form of alkali metal salts,silver salts or organic tertiary amine salts thereof. In this case, theacid and base may be added to the reaction system at the same time sothat the salt described above is produced in situ. In this case, it isdesirable for performance of the reaction to use an inert solvent suchas benzene, acetone, dimethylformamide or the like at the boiling pointof the solvent used or at a lower temperature. As the halogen atom, achlorine or bromine atom is frequently used.

A method for the preparation of the present compounds will beillustrated in more detail with reference to the following examples.

EXAMPLE 1

Preparation of 4-methylocta-4-ene-1,7-diyne-3-ylα-isopropyl-4-chlorophenylacetate (1)

1.40 Grams (11.4 millimoles) of 4-methylocta-4-ene-1,7-diyne-3-ol isdissolved in 20 ml of a dry benzene, followed by cooling in ice water.Thereafter, 1.80 g (22.8 millimoles) of pyridine is rapidly addedthereto at a time and immediately a solution of 2.64 g (11.4 millimoles)of α-isopropyl-4-chlorophenylacetyl chloride in 10 ml of dry benzene isdropwise added thereto for about 30 minutes with stirring. Aftercompletion of the addition, stirring is continued for 3 hours at roomtemperature to complete the reaction. The reaction mixture is pouredinto 20 g of ice water and the layers are separated. The aqueous layeris extracted with two 10-ml portions of ether. The organic layersobtained is combined and washed once with a 10% hydrochloric acid andthree times with water, followed by drying over anhydrous sodiumsulfate. After the solvent is removed under reduced pressure, the oilysubstance obtained is mixed with almost the same amount of pyridine. Themixture is adsorbed to 100 g of silica gel column and purified bydeveloping with a mixed solvent (18 : 1 : 1) of carbon tetrachloride :n-hexane : ether. Thus, 3.19 g of the objective ester is obtained as apale yellow oily substance (85.1% of theoretical yield). n_(D) ²³.01.5233

EXAMPLE 2

Synthesis of 4-methylocta-4-ene-1,7-diyne-3-ylα-isopropyl-3,4-dichlorophenylacetate (2)

By the same procedure as in Example 1, 1.22 g (10.0 millimoles) of4-methylocta-4-ene-1,7-diyne-3-ol, 2.66 g (10.0 millimoles) ofα-isopropyl-3,4-dichlorophenylacetyl chloride and 1.58 g (20.0millimoles) of pyridine are reacted, followed by purification on silicagel column. Thus, 3.18 g of the objective ester is obtained as a paleyellow oily substance (87.5% of theoretical yield). n_(D) ²⁴.0 1.5314

EXAMPLE 3

Synthesis of 4-methylocta-4-ene-1,7-diyne-3-ylα-isopropyl-3,4-tetramethylenephenylacetate (5)

11.61 g (50 millimoles) of α-isopropyl-3,4-tetramethylenephenylaceticacid and 6.11 g (50 millimoles) of 4-methylocta-4-ene-1,7-diyne-3-ol aredissolved in 100 ml of a dry benzene. Thereafter, 16.51 g (80millimoles) of dicyclohexyl carbodiimide is added thereto and theresulting mixture is allowed to stand overnight in a tightly sealedflask. Next day, the reaction mixture is heated under reflux for 4 hoursto complete the reaction. After cooling, the precipitated dicyclohexylurea is filtered off.

The filtrate is concentrated and the viscous oily substance obtained isadsorbed, together with almost the same amount of pyridine, to 350 g ofsilica gel column and developed by passing through a mixture ofchloroform : n-hexane (12 : 1) as a developing solvent. Thus, 10.63 g ofthe objective ester is obtained as a pale yellow oily substance (61.0%of theoretical yield). n_(D) ²³.5 1.5196

EXAMPLE 4

Synthesis of 6-phenyl-4-methylhexa-4-ene-1-yne-3-ylα-isopropyl-4-fluorophenylacetate (12)

7.11 Grams (20 millimoles) of α-isopropyl-4-fluorophenylacetic anhydrideand 1.86 g (10 millimoles) of 6-phenyl-4-methylhexa-4-ene-1-yne-3-ol aredissolved in 30 ml of a dry pyridine. The resulting solution is stirredovernight at room temperature. Next day, the reaction solution is pouredinto 100 g of ice water and extracted with three 30-ml portions ofether. The ether layers obtained are combined and extracted twice withan aqueous saturated sodium hydrogen carbonate. Thereafter, the etherlayer is further washed once with a 10% aqueous hydrochloric acid andthree times with water, followed by drying over anhydrous sodiumsulfate.

After distilling off the ether under reduced pressure, the crude esterobtained is adsorbed to 120 g of silica gel column and eluted with amixed solvent of chloroform : n-hexane (8 : 1). Thus, 2.13 g of theobjective ester is obtained as a pale yellow oily substance (58.4% oftheoretical yield). n_(D) ²⁵.5 1.5118

In the same manner as described above, the compounds of the followingtable were obtained. In the table, a, b and c in the column ofesterification method have the following meanings,

a: Esterification using acid chlorides

b: Esterification using acid anhydrides

c: Esterification using acids and dicyclohexyl carbodiimide

and (C) and (F) in the column of elementary analysis mean a calculatedvalue and found value, respectively.

      Com-      pound  Esterifica- Refractive Yield Elementary analysis No.     Formula Name tion method index (%) C(%) H(%) N(%) X(%) S(%)                  1      ##STR7##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-4-chlorophenylacetat     e a n.sub.D.sup.23.0 1.5233 85.1 (F) 72.91(C) 73.05as C.sub.20 H.sub.21     O.sub.2 Cl 6.506.44 ---- 10.17(Cl)10.78(Cl) ----      2     ##STR8##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-3,4-dichlorophenyl-a     cetate a n.sub.D.sup.24.0 1.5314 87.5 (F) 66.20(C) 66.12as C.sub.20     H.sub.20 O.sub.2 Cl.sub.2 5.595.55 ---- 20.60(Cl)19.52(Cl) ----  3      ##STR9##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-4-methoxyphenylaceta     te b n.sub.D.sup.24.0 1.5183 69.7 (F) 77.66(C) 77.75as C.sub.21 H.sub.24     O.sub.3 7.547.46 ---- -- -- ----      4     ##STR10##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-3,4-methylenedioxyph     enyl-acetate a n.sub.D.sup.23.5 1.5273 86.5 (F) 74.31(C) 74.53as     C.sub.21 H.sub.22 O.sub.4 6.706.55 ---- ---- ----      5     ##STR11##      4-Methylocta-4-ene-1,7-diyne-3-yl α -isopropyl-3,4-tetramethylenep     henyl-acetate c n.sub.D.sup.23.5 1.5196 61.0 (F) 82.88(C) 82.72as     C.sub.24 H.sub.28 O.sub.2 8.098.10 ---- ---- ----      6     ##STR12##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(5-methyl-3-furyl)-isovalerate a     n.sub.D.sup.23.5 1.5233 88.1 (F) 76.52(C) 76.48as C.sub.19 H.sub.22     O.sub.3 7.397.43 ---- ---- ----      7     ##STR13##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(5-methyl-3-thienyl)-isovalerate a     n.sub.D.sup.25.0 1.5341 78.7 (F) 72.44(C) 72.57as C.sub.19 H.sub.22     O.sub.2 S 7.117.05 ---- ---- 10.3510.20      8     ##STR14##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(5-chloro-2-thienyl)-isovalerate a     n.sub.D.sup.24.0 1.5446 76.4 (F) 64.49(C) 64.56as C.sub.18 H.sub.19     O.sub.2 SCl 5.665.72 ---- 10.33(Cl)10.59(Cl)  9.61 9.58      9     ##STR15##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(2-furyl)-isovalerate a n.sub.D.sup.2     3.5 1.5235 60.7 (F) 76.42(C) 76.48as C.sub.18 H.sub.20 O.sub.3 7.507.43     ---- ---- ----      10     ##STR16##      4-Ethylocta-4-ene-1,7-diyne-3-yl α-isopropyl-4-chlorophenylacetate      a n.sub.D.sup.23.5 1.5246 81.5 (F) 73.61(C) 73.56as C.sub.21 H.sub.23     O.sub.2 Cl  6.696.76 ---- 10.66(Cl)10.34(Cl) ----      11     ##STR17##      4-Methylnona-4-ene-1,8-diyne-3-yl α-isopropyl-4-bromophenylacetate      b n.sub.D.sup.24.0 1.5366 81.3 (F) 65.08(C) 65.12as C.sub.21 H.sub.23     O.sub.2 Br 6.015.98 ---- 20.57(Br)20.63(Br) ----      12     ##STR18##      6-Phenyl-4-methylhexa-4-ene-1-yne-3-yl α-isopropyl-4-fluoro-phenyl     acetate b n.sub.D.sup.25.5 1.5118 58.4 (F) 78.98(C) 79.09as C.sub.24     H.sub.25 O.sub.2 F 6.876.91 ---- -- 5.21(F) ----      13     ##STR19##      4-Methylocta-4,7-diene-1-yne-3-yl α-isopropyl-4-chlorophenylacetat     e a n.sub.D.sup.24.0 1.5277 90.6 (F) 72.93(C) 72.60as C.sub.20 H.sub.23     O.sub.2 Cl 6.427.01 ---- 10.81(Cl)10.72(Cl) ----      14     ##STR20##      4-Methylnona-4,8-diene-1-yne-3-yl α -isopropyl-4-methoxyphenylacet     ate a n.sub.D.sup.23.8 1.5206 88.7 (F) 77.58(C) 77.61as C.sub.22     H.sub.28 O.sub.3 8.308.29 ---- ---- ----      15     ##STR21##      1-Phenyl-2-methylpenta-1-ene-4-yne-3-yl α-isopropyl-4-fluorophenyl     -acetate a n.sub.D.sup.24.0 1.5479 89.3 (F) 78.80(C) 78.83as C.sub.23     H.sub.23 O.sub.2 F 6.556.62 ---- -- 5.42(F) ----      16     ##STR22##      4-Chloro-6-phenylhexa-4-ene-1-yne-3-yl α-ethyl-4-bromophenylacetat     e a n.sub.D.sup.24.5 1.5644 87.6 (F) 61.41(C) 61.20 asC.sub.22 H.sub.20     O.sub.2 ClBr 4.544.67 ---- ---- ----      17     ##STR23##      4-Methylocta-4-ene-1,7-diyne-3-yl α-cyclopropyl-4-methylphenylacet     ate a n.sub.D.sup.26.0 1.5517 86.2 (F) 82.40(C) 82.32as C.sub.21     H.sub.22 O.sub.2 7.367.42 ---- ---- ----      18     ##STR24##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-3-methoxycarbonylphe     nyl-acetate an.sub.D.sup.25.5 1.5228 45.6 (F) 74.89(C) 74.97as C.sub.22     H.sub.24 O.sub.4 6.926.86 ---- ---- ----      19     ##STR25##      4-Methylocta-4-ene-1,7-diyne-3-yl α-t-butyl-3,4-dimethoxyphenyl-ac     etate a n.sub.D.sup.25.0 1.5367 81.5 (F) 75.10(C) 74.97as C.sub.23     H.sub.28 O.sub.4 7.587.66 ---- -- -- ----      20     ##STR26##      4-Methylocta-4-ene-1,7-diyne-3-yl α-allyl-4-isopropoxyphenylacetat     e a n.sub.D.sup.23.0 1.5422 66.6 (F) 78.80(C) 78.82as C.sub.23 H.sub.26     O.sub.3 7.507.48 ---- ---- ----      21     ##STR27##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-4-t-butylphenylaceta     te c n.sub. D.sup.24.5 1.5442 59.4 (F) 82.17(C) 82.24as C.sub.24     H.sub.30 O.sub.2 8.748.63 ---- ---- ----      22     ##STR28##      4-Methylocta-4,7-diene-1-yne-3-yl α-cyclohexyl-phenylacetate a     n.sub.D.sup.23.0 1.5122 85.4 (F) 82.16(C) 82.10as C.sub.23 H.sub.28     O.sub.2 8.468.39 ---- ---- ----      23     ##STR29##      4-Methylnona-4-ene-1,8-diyne-3-yl α-ethyl-4-cyanophenylacetate a     n.sub.D.sup.25.0 1.5225 57.4 (F) 79.02(C) 78.97as C.sub.21 H.sub.21     O.sub.2 N 6.556.63 4.294.39 ---- ----      24     ##STR30##      Octa-4-ene-1,7-diyne-3-yl α-isopropyl-4-chlorophenylacetate b     n.sub.D.sup.25.0 1.5247 60.8 (F) 72.46(C) 72.49as C.sub.19 H.sub.19     O.sub.2 Cl 6.016.08 ---- 11.35(Cl)11.26(Cl) ----      25     ##STR31##      4-Ethylnona-4,8-diene-1-yne-3-yl α-propargyl-4-ethylphenylacetate     a n.sub.D.sup.25.0 1.5417 89.5 (F) 82.66(C) 82.72as C.sub.24 H.sub.28     O.sub.2 8.088.10 ---- ---- ----      26     ##STR32##      4-Methylocta-4-ene-1,7-diyne-3-yl α-cyclopropyl-methyl-4-ethoxyphe     nyl-acetate a n.sub.D.sup.27.5 1.5298 87.7 (F) 78.76(C) 78.82as C.sub.23     H.sub.26 O.sub.3 7.527.48 ---- ---- ----      27     ##STR33##      5-Phenylpenta-4-ene-1-yne-3-yl α-isopropyl-4-methylthiophenyl-acet     ate b n.sub.D.sup.25.0 1.5471 60.1 (F) 75.33(C) 75.29as C.sub.23     H.sub.24 O.sub.2 S 6.706.64 ---- ---- 8.848.79      28     ##STR34##      4-Methylocta-4,7-diene-1-yne-3-yl α-propyl-4-nitrophenylacetate a     n.sub.D.sup.24.5 1.5544 61.6 (F) 70.33(C) 70.36as C.sub.20 H.sub.23     O.sub.4 N 6.826.794.304.10 ---- ----      29     ##STR35##      4-Methylocta-4-ene-1,7-diyne-5-yl 2-(4,5,6,7-tetrahydro-2-benzothienyl)-     isovalerate a n.sub.D.sup.23.0 1.5629 79.5 (F) 74.48(C) 74.53as C.sub.22     H.sub.26 O.sub.2 S 7.417.39 ---- ---- 8.929.05      30     ##STR36##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(4,5-tri-methylene-thienyl)-isovaler     ate a n.sub.D.sup.24.5 1.5576 73.7 (F) 74.16(C) 74.08as C.sub.21     H.sub.24 O.sub.2 S 7.18 7.10 ---- ---- 9.609.42      31     ##STR37##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(2-benzo-thienyl)-isovalerate a     n.sub.D.sup.26.0 1.5735 83.4 (F) 75.37(C) 75.39as C.sub.22 H.sub.22     O.sub.2 S 6.426.33 ---- ---- 9.029.15      32     ##STR38##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(3-benzo- thienyl)-isovalerate a     n.sub.D.sup.24.0 1.5699 80.9 (F) 75.30(C) 75.39as C.sub.22 H.sub.22     O.sub.2 S 6.376.33 ---- ---- 9.209.15      33     ##STR39##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(5-indanyl)-isovalerate a n.sub.D.su     p.23.5 1.5427 85.9 (F) 82.66(C) 82.59as C.sub.23 H.sub.26 O.sub.2     7.997.84 ---- ---- ----      34     ##STR40##      4-Methylocta-4-ene-1,7-diyne-3-yl 2-(2-benzo-furyl)-isovalerate a     n.sub.D.sup.25.0 1.5366 64.3 (F) 79.00(C) 79.01as C.sub.22 H.sub.22     O.sub.3 6.706.63 ---- --------       35     ##STR41##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-4-acetylphenylacetat     e a n.sub.D.sup.25.0 1.5318 77.6 (F) 78.62(C) 78.54as C.sub.22 H.sub.24     O.sub.3 7.247.19 ---- ---- ----      36     ##STR42##      4-Methylocta-4-ene-1,7-diyne-3-yl α-isopropyl-3-vinylphenylacetate      a n.sub.D.sup.26.5 1.5633 70.0 (F) 82.51(C) 82.46as C.sub.22 H.sub.24     O.sub.2 7.547.55 ---- ---- ----      37     ##STR43##      4-Chloro-6-phenylhexa-4-ene-1-yne-3-yl α-isopropyl-4-acetyloxy-phe     nylacetate a n.sub.D.sup.24.0 1.5416 67.8 (V) 70.49(C) 70.66as C.sub.25     H.sub.25 O.sub.4 Cl 6.025.93 ---- 8.41(Cl)8.34(C) ----      38     ##STR44##      4-Methylnona-4,8-diene-1-yne-3-yl α-isopropyl-3,4-methylenedioxyph     enyl-acetate a n.sub.D.sup.25.0 1.5288 88.1 (F) 74.52(C) 74.55as     C.sub.22 H.sub.26      O.sub.4 7.317.39 ---- ---- ----

The substituted-arylacetic acid esters of the present invention whichare represented by the formula (I) have both a rapid effect and anexcellent insecticidal activity. Further, the esters are expected toexhibit a repelling effect on mites and a synergistic effect togetherwith other compounds having a biological activity. Still further, theesters are widely used as compositions for controlling insects injuriousto agriculture, horticulture, forestry, sanitation and stored cerealsand mites, and are available at low cost.

In the practical application of these compounds, they may be appliedalone or in combination with suitable amounts of one or more of solvent,filler, diluent, active agent, dispersing agent, surface active agent,wetting agent, pressure-applying agent, emulsifying agent and attractantand used in the form of emulsifiable concentrates, wettable powders,dusts, granules, fine granules, powdered granules, coatings, oil sprays,aerosols, mosquito coils, fumigants, heating fumigants, electricmosquito killers, baits and the like.

The excellent effects of the present compounds will become more apparentby the following experimental examples.

Experimental Example 1

An emulsifiable concentrate is prepared by blending 30% of each of thepresent compounds (1) to (35), 50% of xylene and 20% of Sorpol SM-200 (aregistered trade mark of Toho Kagaku Co.).

The emulsifiable concentrates thus formulated were diluted 300 timeswith water. In the same manner, commercially available 30% wettablepowder, Carbaryl (1-naphthyl-N-methylcarbamate) was diluted as acontrol. Each test solution thus prepared was individually sprayed onthe rice plants in a pot which had elasped 25 days after sowing, in aproportion of 10 ml/pot. Thereafter, each pot was covered with acylindrical wire net and 15 green rice leafhoppers (Nephotettixcincticeps) were liberated in the pot. After one day, the death andalive were observed and as the result, a mortality of more than 90% wasobtained with a every present compound and Carbaryl.

Experimental Example 2

An emulsifiable concentrate is prepared by blending 20 parts of each ofthe following present compounds, 60 parts of xylene and 20 parts ofSorpol SM-200 (a registered trade mark of Toho Kagaku Co.). Thefollowing compounds as a control are also treated in the same manner asdescribed above.

The emulsifiable concentrates thus formulated were diluted with water toa required concentration. Each test solution thus prepared wasindividually sprayed on the rice plants in a pot which had elapsed 25days after sowing, in a proportion of 10 ml/pot. Thereafter, each potwas covered with a cylindrical wire net and 15 smaller brownplanthoppers (Laodelphax striatellus) were liberated in the pot. Afterone day, the death and alive were observed and the value of LC₅₀ ofevery concentrate was obtained from the mortality.

The compounds of the present invention are expressed by the foregoingcompound number. The experimental results are shown in the followingtable.

    ______________________________________                                                                    LC.sub.50                                         Test compound               (PPM)                                             ______________________________________                                        Present compound                                                                            (1)               23                                            "             (2)               31                                            "             (3)               35                                            "             (4)               28                                            "             (6)               32                                            "            (10)               34                                            "            (14)               46                                            "            (19)               43                                            "            (23)               50                                            "            (27)               66                                            "            (29)               48                                            "            (32)               50                                             ##STR45##                  87                                                 ##STR46##                  68                                                 ##STR47##                  73                                                  Hopcide .sup.1)           75                                                 Sevin .sup.2)              193                                               ______________________________________                                         ##STR48##                                                                     ##STR49##                                                                    *The compound disclosed in British Patent Publication                          No. 1439615                                                              

Each of the following present compounds is formulated into a 0.1% oilspray using deodorized kerosene. The following compounds as a controlare also likewise treated.

About 50 house-fly adults (Musca domestica) are liberated in a (70 cm)³glass chamber. Thereafter, 0.7 ml of each oil spray is sprayed under apressure of 1.5 kg/cm² and the knock-down of the insects with the lapseof time is observed. This test is repeated several times with each oilspray to obtain the values of KT₅₀ (time required for 50% knock-down) asshown in the following table. The present compounds are indicated by theforegoing compound number.

    ______________________________________                                                                    KT.sub.50                                         Test compound               (second)                                          ______________________________________                                        Present compound                                                                            (1)               128                                           "             (3)               139                                           "             (4)               136                                           "             (5)               140                                           " (7)        175                                                              "            (11)               147                                           "            (14)               174                                           "            (23)               140                                           "            (30)               158                                           "            (34)               170                                            ##STR50##                  510                                                ##STR51##                  183                                                ##STR52##                  490                                                Allethrin.sup.3)           504                                                Resmethrin.sup.4)          >600                                               Pyrethrins                 180                                               ______________________________________                                         ##STR53##                                                                     ##STR54##                                                                     *The compound disclosed in British Patent Publication No. 1439615        

Experimental Example 4

Each of the following present compounds is formulated into a 0.2% oilspray using deodorized kerosene. The compounds as a control are alsolikewise treated.

Nylon net of about 15 mesh is set up at the bottom of a glass cylinder(20 cm in diameter and 20 cm in height) and butter is coated on theinside wall in a width of about 3 cm at the upper part and twenty Germancockroach adults (Blattella germanica) are liberated therein and anothersame glass cylinder is then placed thereon. 0.5 Ml of each oil spray issprayed into the glass cylinder under a pressure of 0.75 kg/cm² througha glass atomizer. After covering the cylinder, the knock-down of theinsects with the lapse of time is observed. This test is repeatedseveral times with each oil spray to obtain the values of KT₅₀ (timerequired for 50% knock-down) as shown in the following table.

The present compounds are indicated by the foregoing compound number.

    ______________________________________                                                                     KT.sub.50                                                                     (min.                                            Test compound                sec)                                             ______________________________________                                        Present compound                                                                            (1)                5'00"                                        "             (2)                6'10"                                        "             (3)                4'30"                                        "             (4)                3'50"                                        "             (8)                10'10"                                       "            (13)                9'20"                                        "            (15)                13'40"                                       "            (19)                14'00"                                       "            (23)                8'10"                                        "            (29)                12'20"                                       "            (34)                11'50"                                        ##STR55##                   >20'                                              ##STR56##                   >20'                                              ##STR57##                   15'10"                                           ______________________________________                                         * The compound disclosed in British Patent Publication No. 1439615       

As is apparent from the aforesaid experimental results, the compounds ofthe present invention exhibit an excellent biological activity. When thecompounds have an isomer thereof, the activity is further enhanced byresolution of the compounds into the optical isomers thereof. In thisrespect, the compounds of the present invention are very useful forcontrolling insects injurious to agriculture such as, for example, greenrice leafhopper, planthoppers, rice stem borer, armyworms and cutworms,diamond-back moth, cut worm, cabbage worm, Japanese giant silk moth,tortorix, aphids, mealybug and scales and the like; insects injurious tostored cereals such as, for example, rice weevils; and mites.

In particular, the compounds of the present invention are very superiorin that they can freely be used, due to their low toxicity andharmlessness to mammals, for agricultural crops before harvest,household horticulture, green-house cultivation and food-packaging.

In the preparation of the present compositions, it is also possible todevelop a more superior controlling effect by the combined use of two ormore compounds of the present invention. Further, it is possible toobtain multipurpose compositions having a more superior effect byblending with other insecticides and other chemicals. The insecticidesinclude organo-chlorine type insecticides such as DDT, BHC andmethoxychlor; organo-phosphorus type insecticides such as0,0-dimethyl-0-(3-methyl-4-nitrophenyl)-phosphorothioate [hereinafterreferred to as Sumithion (a registered trade mark of Sumitomo ChemicalCo.)], Diazinon, Fenthion, 0,0-dimethyl-0-4-cyanophenyl-phosphorothioate[hereinafter referred to as Cyanox (a registered trade mark of SumitomoChemical Co.)],0,0-dimethyl-S-[α-(ethoxycarbonyl)benzyl]-phosphorodithioate[hereinafter referred to as Papthion (a registered trade mark of BayerCo.)], 2-methoxy-4H-1,3,2-benzodioxaphosphorin-2-sulfide [hereinafterreferred to as Salithion (a registered trade mark of Sumitomo ChemicalCo.)], and 0-ethyl-0-4-cyanophenylphenylphosphonothioate [hereinafterreferred to as Surecide (a registered trade mark of Sumitomo ChemicalCo.)]; carbamate type insecticides such as 1-naphthyl-4-methylcarbamate,3,4-dimethylphenyl-N-methylcarbamate,3,5-dimethylphenyl-N-methylcarbamate and2-isopropoxyphenyl-N-methylcarbamate; pyrethrin, allethrin,N-(3,4,5,6-tetrahydrophthalimido)-methyl chrysanthemate [hereinafterreferred to as Neo-pynamin (a registered trade mark of Sumitomo ChemicalCo.)], 5-benzyl-3-furylmethyl chrysanthemate [hereinafter referred to asCrysron (a registered trade mark of Sumitomo Chemical Co.)],5-propargylfurfurylmethyl chrysanthemate,5-propargyl-2-methyl-3-furylmethyl chrysanthemate, 3-phenoxybenzylchrysanthemate, the geometric and optical isomers thereof, thewell-known cyclopropanecarboxylic esters other than those mentionedabove, and the synergists for them such as piperonylbutoxide, sulfoxide,sufroxane, MGK-264, I.B.T.A. and S-421. The chemicals include thecompounds used for the preparation of heating fumigants such asterephthalic acid, isophthalic acid and BHT; stabilizers such as phenolderivatives, bisphenol derivatives, arylamines (e.g.phenyl-β-naphthylamine, phenyl-β-naphthylamine and condensation productsof phenetidine and acetone) and other well-known antioxidants; and otheragricultural chemicals, for example, insecticides such as Padan,Galecron and Lannate, acaricides, fungicides, nematocides, herbicides,plant regulators, fertilizers and other chemicals.

By the preparation of these multipurpose compositions, it cansufficiently be expected to attain saving in labor and synergisticeffects by the combined use of the chemicals.

The preparation and controlling effect of the present composition willbe illustrated with reference to the following preparation examples andexamples, which are not of course intended to limit the inventionthereto.

Preparation Example 1

To 20 parts of each of the present compounds (1), (2), (3), (4), (5),(8), (10), (11), (14), (18), (19), (21), (23), (28), (30) and (33) areadded 20 parts of Sorpol SM-200 (the same as above) and 60 parts ofxylene. The mixtures are each throughly mixed to make a solution. Thusemulsifiable concentrate of each compound is obtained.

Preparation Example 2

To 15 parts of each of the present compounds (2), (4), (11), (23) and(35) are added 25 parts of natural pyrethrum extracts (pyrethrin content20%), 20 parts of Sorpol SM-200 (the same as above) and 40 parts ofxylene. The mixtures are each thoroughly mixed to make a solution. Thusemulsifiable concentrate of each compound is obtained.

Preparation Example 3

To 20 parts of each of the present compounds (1), (4), (6), (10), (11),(19), (23), (29) and (33) are added 20 parts of Cyanox (the same asabove), 20 parts of Sorpol SM-200 (the same as above) and 40 parts ofxylene. The mixtures are each thoroughly mixed to make a solution. Thusemulsifiable concentrate of each compound is obtained.

Preparation Example 4

To 15 parts of each of the present compounds (2), (8), (13), (20) and(32) are added 25 parts of Sumithion (the same as above), 20 parts ofSorpol SM-200 (the same as above) and 40 parts of xylene. The mixturesare each thoroughly mixed to make a solution. Thus emulsifiableconcentrate of each compound is obtained.

Preparation Example 5

Fifteen parts of each of the present compounds (1) to (35), 15 parts of1-naphthyl-N-methylcarbamate and 5 parts of Sorpol SM-200 (the same asabove) are thoroughly mixed. The mixtures are each mixed with 65 partsof 300 mesh diatomaceous earth in a mortar while thoroughly stirring.Thus wettable powder of each compound is obtained.

Preparation Example 6

One part of each of the present compounds (2), (4), (5), (7), (12),(17), (20), (21), (22), (25), (26), (32) and (35) and 5 parts ofpiperonyl-butoxide are dissolved in 20 parts of acetone, and then 94parts of 300 mesh talc are added thereto. After thoroughly mixing in amortar while stirring, acetone is removed by evaporation. Thus dust ofeach compound is obtained.

Preparation Example 7

0.1 Part of each of the present compounds (1), (4) and (29) is dissolvedin kerosene to become a total weight of 100 parts. Thus oil spray ofeach compound is obtained.

Preparation Example 8

0.1 part of each of the present compounds (2), (5), (8), (12), (17),(23), (29) and (35), 0.1 part of Neo-pynamin (the same as above) and 0.8part of S-421 are dissolved in kerosene to become a total weight of 100parts. Thus oil spray of each compound is obtained.

Preparation Example 9

0.1 Part of each of the present compounds (3), (9), (11), (15), (20),(22), (25), (30) and (34), 0.1 part of d-trans chrysanthemic ester ofallethrin and 0.6 part of piperonyl-butoxide are dissolved in keroseneto become a total weight of 100 parts. Thus oil spray of each compoundis obtained.

Preparation Example 10

0.2 Part of each of the present compounds (1), (4), (8) and (23), 0.2part of 2-isopropoxyphenyl N-methylcarbamate and 5 parts of xylene aredissolved in kerosene to become a total weight of 100 parts. Thus oilspray of each compound is obtained.

Preparation Example 11

Each of the insecticidal groups comprising the active ingredients in acomposition shown in the following recipes is dissolved in a mixedsolvent of xylene and purified kerosene (1 : 1) to become a total weightof 15 parts. The solutions are each filled in an aerosol container.After attaching a valve portion to the container, 85 parts of apropellent (e.g. freon, vinylchloride monomer, liquefied petroleum gas)is charged therein under pressure through the valve. Thus aerosol ofeach compound is obtained.

    ______________________________________                                        Recipe of aerosol formulation                                                 Recipe  Composition                                                           ______________________________________                                        A       present compound (1)                                                                              0.3 part                                                  3-phenoxybenzyl d-cis,trans                                                   chrysanthemate      0.1 part                                          B       present compound (1)                                                                              0.4 part                                                  piperonyl-butoxide  2.0 parts                                         C       present compound (2)                                                                              0.3 part                                                  DDVP                0.3 part                                          D       present compound (3)                                                                              0.2 part                                                  d-trans chrysanthemic ester                                                   of allethrin        0.2 part                                                  sufroxane           2.0 parts                                         E       present compound (4)                                                                              0.2 part                                                  Neo-pynamin         0.2 part                                                  piperonyl-butoxide  2.0 parts                                         F       present compound (4)                                                                              0.3 part                                                  Neo-pynamin         0.2 part                                                  I.B.T.A.            1.0 part                                          G       present compound (13)                                                                             0.2 part                                                  Neo-pynamin         0.2 part                                                  Sumithion           0.3 part                                          H       present compound (23)                                                                             0.2 part                                                  Neo-pynamin         0.2 part                                                  Crysron             0.1 part                                          I       present compound (28)                                                                             0.2 part                                                  d-cis, trans chrysanthemic                                                    ester of allethrin  0.2 part                                                  sufroxane           2.0 parts                                         J       present compound (33)                                                                             0.3 part                                                  d-trans chrysanthemic ester                                                   of allethrin        0.2 part                                          ______________________________________                                    

Preparation Example 12

Each of the insecticidal groups comprising the active ingredients in acomposition shown in the following recipes is dissolved in 20 ml ofmethanol. To each solution is added a mosquito coil carrier (containingTabu powder, pyrethrum marc and wood powder in a ratio of 3 : 5 : 1) tobecome a total weight of 100 g. The mixtures are each thoroughly mixedwhile stirring and then the methanol is evaporated. To the residueobtained is added 150 ml of water and the mixture is kneaded thoroughly,shaped into a mosquito coil and dried. Thus mosquito coil of eachcompound is obtained.

    ______________________________________                                        Recipe of mosuito coil formulation                                            Recipe  Composition                                                           ______________________________________                                        A       present compound (1)                                                                              0.3 g                                                     allethrin           0.2 g                                                     BHT                 0.3 g                                             B       present compound (3)                                                                              0.3 g                                                     d-trans chrysanthemic ester                                                   of allethrin        0.1 g                                                     BHT                 0.4 g                                             C       present compound (4)                                                                              0.2 g                                                     5-propargylfurfuryl                                                           chrysanthemate      0.2 g                                                     BHT                 0.8 g                                             D       present compound (19)                                                                             0.3 g                                                     5-propargyl-2-methyl-3-                                                       furylmethyl chrysanthemate                                                                        0.1 g                                                     BHT                 0.4 g                                             ______________________________________                                    

Preparation Example 13

Each of the insecticidal groups comprising the active ingredients in acomposition shown in the following recipes is dissolved in a suitableamount of chloroform. The solutions are each adsorbed uniformly to thesurface of asbestos (2.5 cm × 1.5 cm in size and 0.3 mm in thickness),and then asbestos of the same size is struck thereon. Thus fibrousheating fumigant insecticidal composition for use on a heater of eachcompound is obtained. Pulp plate may be used as a fibrous carrier havingthe same effect in place of asbestos.

Recipe for the formulation of heating fumigant for use on a heater

    Recipe for the formulation of heating                                         fumigant for use on a heater                                                  Recipe  Composition                                                           ______________________________________                                        A       present compound (1)                                                                              0.05 g                                                    allethrin           0.02 g                                                    piperonyl-butoxide  0.07 g                                            B       present compound (4)                                                                              0.07 g                                                    d-trans chrysanthemic ester                                                   of allethrin        0.01 g                                                    piperonyl-butoxide  0.1 g                                             C       present compound (5)                                                                              0.05 g                                                    5-propargyl-2-furylmethyl                                                     chrysanthemate      0.02 g                                                    piperonyl-butoxide  0.15 g                                                    BHT                 0.1 g                                             D       present compound (10)                                                                             0.05 g                                                    5-propargyl-2-methyl-3-                                                       furylmethyl chrysanthemate                                                                        0.02 g                                                    piperonyl-butoxide  0.15 g                                            E       present compound (23)                                                                             0.04 g                                                    allethrin           0.04 g                                                    piperonyl-butoxide  0.08 g                                                    BHT                 0.1 g                                             ______________________________________                                    

Preparation Example 14

To 2 parts of each of the wettable powders formulated according toPreparation Example 6 is added 98 parts of corn meal and then mixedthoroughly to obtain a bait. The bait is applied as it is in a practicaluse.

Preparation Example 15

Five parts of each of the present compounds (1) to (35), 5 parts ofsodium ligninsulfonate, 85 parts of Fubasami clay and 5 parts of waterare thoroughly kneaded, granulated by means of a granulator and dried.Thus granular preparation of each compound is obtained. The granularpreparation is applied as it is in a practical use.

The insecticidal effect of the thus obtained present compositions oninsects injurious to cereals will be illustrated with reference to thefollowing examples.

EXAMPLE 5

Each of the emulsifiable concentrates formulated according toPreparation Example 1 was diluted 200 times with water. Ten larvae oftabacco cut worm (Spodoptera litura) in the third instar stage wereliberated in a glass Petri dish of 14 cm in diameter and 1 ml of eachtest solution thus prepared was sprayed from the spraying tower.Thereafter, the larvae were liberated in another dish in which feed hadpreviously been placed. After two days, more than 80% of the larvae werekilled with any concentrate.

EXAMPLE 6

Each of the emulsifiable concentrates formulated according toPreparation Example 2 was diluted 200 times with water. Each testsolution thus prepared was sprayed on the field, in a proportion of 100l/tan, wherein radish had been grown up to a 5- to 6-leaf stage over thewhole surface and a numerous number of green peach aphids (Myzuspersicae) had been made parasitic on the leaves of the radish. After twodays, a density of parasitism was checked and it was found that thedensity was reduced to less than one-tenth of its initial value in everyplot.

EXAMPLE 7

Each of the emulsifiable concentrates formulated according toPreparation Example 3 was diluted 200 times with water. A plywood of 15cm × 15 cm in size was coated with each test solution thus prepared in aproportion of 50 ml/m² and air-dried. Thereafter, German cockroachadults (Blattella germanica) were brought into contact with the plywoodfor 1 hour. After three days, more than 80% of the test insects werekilled with any concentrate.

EXAMPLE 8

Each of the emulsifiable concentrates formulated according toPreparation Example 4 was diluted 200 times with water. Each testsolution thus prepared was sprayed on a eggplant (grown-up) field, in aproportion of 100 l/tan, on which a numerous number of 28-spotted ladybettle larvae (Epilachna vigintioctopunctata) were made parasitic. After30 minutes, knock-down of the insect in every plot was checked and itwas found that more than 90% of the larvae fell down to the ground.After 24 hours, the density of parasitism was checked and it was foundthat a control effect close to 100% was obtained in every plot incomparison with that obtained with a control plot.

EXAMPLE 9

Each of the wettable powders formulated according to Preparation Example5 was diluted 400 times with water. Each test solution thus prepared wassprayed on the rice plants in a 1/50,000 Wagner pot which had elapsed 45days after sowing, in a proportion of 10 ml/pot. Thereafter, each potwas covered with a cylindrical wire net and about 20 smaller brownplanthopper adults (Laodelphax striatellus) were liberated in the pot.After one day, more than 80% of the test insects were killed with anywettable powder.

EXAMPLE 10

Each of the dusts formulated according to Preparation Example 6 wasuniformly dusted on the bottom of a glass Petri dish of 14 cm indiameter, in a proportion of 2 g/m². The dish was coated on the insidewall with butter, leaving at the lower part an uncoated portion of 1 cmin width.

Thereafter, 10 German cockroach adults (Blattella germanica) per groupwere liberated in the dish and allowed to come into contact with thedust for 30 minutes. The test insects were then moved to another dish.After three days, more than 80% of the adults were killed with any dust.

EXAMPLE 11

Five milliliters of each of the oil sprays formulated according toPreparation Example 7 was sprayed, using Campbel's turn table apparatus[Soap and Sanitary Chemicals, Vol. 14, No. 6, 119 (1938)]. Twentyseconds after spraying, the shutter was opened, and about 100 house-flyadults (Musca domestica) per group were exposed to the descending mistfor 10 minutes. The flies were then fed and allowed to stand. Next day,more than 80% of the house-fly were killed with any oil spray.

EXAMPLE 12

About 50 house-fly adults (Musca domestica) were liberated in a (70 cm)³glass chamber. Thereafter, 0.7 ml of each of the oil sprays formulatedaccording to Preparation Example 8 was sprayed in the chamber under apressure of 1.5 kg/cm². After 10 minutes, more than 80% of the flieswere knocked down.

EXAMPLE 13

About 50 northern house mosquito adults (Culex pipiens pallens) wereliberated in a (70 cm)³ glass chamber. Thereafter, 0.7 ml of each of theoil sprays formulated according to Preparation Example 9 was sprayed inthe chamber under a pressure of 1.5 kg/cm². After 10 minutes, more than80% of the mosquitos were knocked down.

EXAMPLE 14

Nylon net of about 15 mesh was set up at the bottom of a glass cylinder(20 cm in diameter and 20 cm in height) and butter was coated on theinside wall thereof in a width of about 3 cm at the upper part. TwentyGerman cockroach adults (Blattella germanica) were liberated therein.

The glass cylinder containing the cockroaches was piled on another sameglass cylinder and further a glass cylinder (20 cm in diameter and 40 cmin height) was piled on the former glass cylinder. Thereafter, 0.5 ml ofeach of the oil sprays formulated according to Preparation Example 10was sprayed into the cylinder at the top thereof under a pressure of0.75 kg/cm² through a glass atomizer. After covering the cylinder, theadults were allowed to stand. After three days, more than 90% of thetest insects were killed.

EXAMPLE 15

The insecticidal activity on house-fly adults (Musca domestica) of theaerosols formulated according to Preparation Example 11 was tested bythe aerosol test method (Soap and Chemical Specialities, Blue Book,1965) using Peet Grady's chamber. Thus, with any aerosol, more than 80%of the flies were knocked down 15 minutes after spraying and more than70% of the flies were killed by the next day.

EXAMPLE 16

About 50 northern house mosquito adults (Culex pipiens pallens) wereliberated in a (70 cm)³ glass chamber. One gram of each of the mosquitocoils formulated according to Preparation Example 12 was ignited at theboth ends and placed at the center of the bottom of the chamber. After20 minutes, more than 80% of the mosquitos were knocked down.

EXAMPLE 17

About 50 northern house mosquito adults (Culex pipiens pallens) wereliberated in a (70 cm)³ glass chamber. Each of the heating fumigantcompositions formulated according to Preparation Example 13 were placedon a heater in the chamber and fumigated. More than 90% of the mosquitoswere knocked down within 20 minutes.

EXAMPLE 18

Among the dusts formulated according to Preparation Example 6, thosecontaining the present compounds (2), (7), (12), (20), (25) and (32)were each dusted, using Belljar duster, on the rice plants in a 1/50,000Wagner pot which had elapsed 45 days after sowing, in a proportion of 3kg/10 are. After covering the pot with wire net, about 30 green riceleafhopper adults (Nephotettix cincticeps) were liberated therein. Afterone day, more than 70% of the test insects were killed.

EXAMPLE 19

Among the emulsifiable concentrates formulated according to PreparationExample 1, those containing the present compounds (1), (3), (4), (10),(14), (21), (28) and (33) were each diluted 500 times with water. Eachtest solution thus prepared was sprayed, by means of a turn table, onthe rice plants in a 1/100,000 Wagner's pot which had been grown up tothe tillering stage.

Thereafter, the eggs just before hatch of rice stem borer (Chilosuppressalis) were inoculated into the rice plants in a proportion of100/pot. After four days, the death and alive of the insect in the riceplant were checked. As the results, the mortality was 100% with anyemulsifiable concentrate.

EXAMPLE 20

Carmine mite female adults (Tetranychus cinnabarinus) were madeparasitic on the leaves of potted kidney beans (2-leaf stage) which hadelapsed 9 days after sowing, in a proportion of 10 - 15/leaf. Afterleaving them as they are for seven days, a numerous number of carminemites were found to be bored at various growth stages. Among theemulsifiable concentrates formulated according to Preparation Example 1,those containing the present compounds (1), (4), (14), (19), (23), (30)and (33) were each diluted 500 times with water. At this time, each testsolution thus prepared was sprayed in a proportion of 10 cc/pot by meansof a turn table. After 10 days, damage of the kidney beans by theinsects was checked. As the results, an increase in the damage was notobserved with any emulsifiable concentrate.

EXAMPLE 21

A green-house (3 m in height) was divided into plots having an area of30 m² and chinese cabbages were grown up therein. Thereafter, armywormsand cutworms, cabbage worm and diamond-back moth were artificially madeparasitic on the cabbages. The present compounds (1), (3) and (4) wereeach dissolved in cellosolve to make a 20% solution. Each test solutionthus prepared was sprayed under pressure on the cabbages so that theamount of the active ingredient becomes 50 g/10 are. Thus, no spread ofdamage by the insect was observed with any compound.

EXAMPLE 22

Ten liters of water were placed in a 14-liter polypropylene bucket, and1 g of each of the granular preparations formulated according toPreparation Example 15 was added thereto. After one day, about 100 fullgrown northern house mosquito larvae (Culex pipiens pallens) wereliberated in the water and the death and alive of the larvae wereobserved. As the results, more than 90% of the larvae were killed with24 hours.

What is claimed is:
 1. A compound of the formula, ##STR58## wherein R₁and R₂ are each hydrogen or a halogen atom, a C₁ -C₄ alkyl, C₂ -C₄alkenyl, nitro, C₁ -C₄ alkanoyl, an C₁ -C₄ alkanoyloxy, or R₁ and R₂,taken together, may form, a C₃ -C₅ alkylene or butadienylene(--CH═CH--CH═CH--) ring; R₃ is a C₂ -C₄ alkyl, C₂ -C₄ alkenyl,propargyl, cyclo C₃ -C₆ alkyl or cyclopropylmethyl group; R₄ is hydrogenor a halogen atom, methyl or ethyl group; R₅ is allyl, propargyl,3-butenyl, 3-butynyl, phenyl or benzyl group; and A is a --CH═CH--group.
 2. The compound according to claim 1, wherein R₁ and R₂ are eachhydrogen, fluorine, chlorine or bromine atom, a C₁ -C₄ alkyl, C₂alkenyl, nitro, acetyl, or acetyloxy, or R₁ and R₂, taken together, mayform tri- or tetra-methylene ring or butadienylene ring; R₃ is a C₂ -C₄alkyl, C₃ -C₆ cycloalkyl, cyclopropylmethyl, allyl or propargyl group;R₄ is hydrogen or chlorine atom, or a C₁ -C₂ alkyl group.
 3. Thecompound according to claim 2 wherein R₁ and R₂ are each hydrogen,fluorine, chlorine or bromine atom, a C₁ -C₄ alkyl, C₂ alkenyl, nitro,acetyl, or acetyloxy or R₁ and R₂, taken together, may form a tri- ortetra-methylene ring;
 4. The compound according to claim 3, which hasthe formula, ##STR59##
 5. The compound according to claim 3, which hasthe formula, ##STR60##
 6. The compound according to claim 3, which hasthe formula, ##STR61##
 7. The compound according to claim 3, which hasthe formula, ##STR62##
 8. The compound according to claim 3, which hasthe formula, ##STR63##
 9. An insecticidal and/or acaricidal compositioncomprising an insecticidally or acaricidally effective amount of acompound according to claim 1 and an inert carrier.
 10. A method forkilling insects or acarids which comprises applying thereto aninsecticidally and/or acaricidally effective amount of a compoundaccording to claim 1.